gilbert



Dec. 15, 1959 A= REAcTIoN PRODUCT oF THE KE-romc cmclwo coMPoUND AND Pc|5 CLOPENTADIENE AND ,MelaI REACTION PRODUCT OF HEXACHLOROCY C =CARBON DISULPHIDE SOLVENT E. E. GILBERT INSECTICIDAL COMPOSITIONS CONTAINING A HEXACHLOROCYCLOPENTADIENE DIMER AND METHOD FOR COMBATING NOXIOUS ORGANISME THEREWITH Original Filed April 6. 1951 United States Patent Ofi-ice Re. 24,750 Reissued Dec. 15, 1959 Everett E. Gilbert, Morris Township, Morris County,

NJ., assignor to Allied Chemical Corporation, a corporation of New York Original No. 2,671,043, dated March 2, 1954, Serial No. 219,740, April 6, 1951. Application for reissue August 19, 1957, Serial No. 679,117

12 Claims. (Cl. 167-30) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

This invention relates to new pesticidal compositions comprising [dodecachlorotetrahydro-4,7-methanoindene] a hexachlorocyclopentadiene dimer as the active toxic ingredient and to a method for combating noxious organisms therewith.

[Dodecachlorotetrahydro-4,7-methanoindene is a] The dimer of hexachlorocyclopentadiene of my invention [which] may be prepared by any suitable process, for exampie by the condensation of hexachlorocyclopentadiene with aluminum chloride as described in J. Am. Chem. Soc; 7l, page 954, March 1949, or by heating [decachlorotetrahydro 4,7 methanoindeneone] the keionic hydrolyzed reaction product of hexachlorocyclo# penzadiene with sulfur trioxide, with PCl5 as described in my copending application Serial No. 219,739, tiled April `6, 1951, now U.S. Patent 2,702,305 according to the reaction indicated below:

carbon atoms, particularly at elevated temperatures. It has high toxicity against many dillicultly controllable noxious organisms including insects and theirlarvae of the orders Lepidoptera (moths), Coleoptera (beetles), Orthoptera (grasshoppers), etc.

The compositions of my invention comprise as the essential toxic ingredient [dodecachlorotetrahydro-4,7 methanoindene, i.e.] the hexachlorocyclopentadiene dimer, which may be applied alone or in association with a fluid or solid carrier material in any suitable manner adapted to combat the particular organism to be controlled. For application as a fluid spray or as an impregnant, the solid [dodecachlorotetrahydro-4,7methano indene] hexachlorocyclopentadene dimer may conveniently be dissolved or dispersed in any standard liquid carrier, such as kerosene orithe like. For application as a dust or spray powder, it may be mixed or milled with a suitable finely divided solid material, such as clay or the like, together with suitable adjuvants, such as wetting and dispersing agents, anticaking agents, antidusting agents, etc., if desired. It may readily be applied from solution in solvents in which it is soluble, for example in acetone, xylene, and aromatic and aliphatic petroleum solvents, or in mixtures or emulsions of such solvents with water or kerosene, together with suitable emulsifying agents. Application of dodecachlorotetrahydro4,7 methanoindene in liquid solution form or emulsion form is especially adapted to moth-proofing of fabrics and the like, while application in the form of dusts, wettable powders, or fluid sprays' in the form of solutions, dispersions, emulsions or the like, may conveniently be used in its application to vegetable crops.

The concentration of [dodecachlorotetrahydro-4,7 methanoindene] the hexachlorocyclopentadiene dimer will vary somewhat with the type of composition, with the organism to be controlled and with surrounding eld In the drawing, the single figure illustrates the infrared spectrogram of the hexachlorocyclopentadiene dimer which comprises the active toxic ingredient of the pesticidal compositions of the invention. The compound prepared by the reaction of PC15 with [decachlorotetrahydro-- 4,7-methanoindeneone] the ketonic hydrolyzed reaction product of hexachiorocyclopeniadiene and S03, is shown as broken line A in the figure, the compound prepared by condensation of hexachlorocyclopentadiene with AlCl3 is shown as solid line B while the carbon disulfide solvent appears as solid line C. The two spectrograms A and B are substantially identical, hence the products prepared by the two processes are identical. The infrared spectrogram of the hexachlorocyclopentadiene dimer has charncieristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns as clearly shown in the drawing.

{Dodecachlorotetrahydro 4,7 methanoindene] The hexachlorocyclopenmdiene dimer of my invention is a white crystalline solid which sublimes without melting at temperatures above about 240 C., soluble in benzene, acetone, kerosene and carbon tetrachloride, etc., and while Virtually insoluble in methanol, is appreciably soluble in thevlower aliphatic alcohols having 2 or more of toxicant inmy new compositions give 4effective insecticidal control in many cases as indicated in the following tables. My compositions, however, will preferably contain at' least about 0.5% 0fl [dodecachlorotetrahydro- 4,7emethanoindene] the hexaclzlorocyclopentadiene dimer based on the solids content ofthe compositions. Usually concentrations between about 0.5% and about 30% are satisfactory. These compositions may be diluted somewhat in application as indicated in the tables, especially in the case of the wettable spray powders, and doses applied will vary according to the particular organisms to be controlled, eld conditions, etc., as known in the art.

The pesticidal electiveness of the hexachlorocyclopentadiene dimer is indicated by the following tests.

In Table I below are shown the results of two tests carried out on southern armyworms (Prodenia eridania (Cram.)). In carrying out these tests, leaves of cranberry bean plants were dipped in an agitated suspension of a wettable spray powder prepared by mixing equal parts of clay and [dodecachlorotetrahydro-4,7-methanoindene] the. hexachlorocyclopentadene dimer (abbreviated as [DTM] H CPD i-n the table) and a small amount of a wetting agent, and dispersing the resulting wettable spray powder in water inthe proportion of one pound of powder per gallons of water. After dipping, the

leaves were withdrawn, and, in the first of the two tests, were dried three hours and then ve 6th instar larvae were confined on the treated plants. Results show percent of larvae dead four days after'infestation.

The second test was carried out in the same manner,

yexcept that plants were allowed to stand two days after dipping before infestation with larvae in order to determine the residual toxicity of the toxicant.

The results are indicated below:

TABLE I Toxicity of [dodecachlorotetrahydro-4,7methanoindene] the hexachlorocyclopentadiene dimer to armyworms Table II below shows the results of field tests with '[dodecachlorotetrahydro-4,7methanoindene] the hexalchlorocyclopemaldene dimer on grasshoppers infesting red clover in comparison with a commercial chlorinated hydrocarbon chlordane recommended as highly toxic to grasshoppers. In carrying out the tests, 1200 sq. ft. of

y clover, infested with three species of grasshopper (redlegged, melanoplus femur-rubrum; lesser migratory, Melanoplus Mexicanus and the two-striped Melanoplus bivittatus, the dominant species being the redlegged), was sprayed with a suspension prepared by mixing clay and [dodecachlorotetrahydro-4,7methanoindene] the hexachlorocyclopentadiene dimer, in the proportion of three parts clay to one part [dodecachlorotetrahydro-4,7-methanoindene] dimer, with a small quantity of a wetting agent and dispersing the resulting wettable spray powder in water in proportion of four pounds of the powder (one pound active toxicant) in 100 gallons of water. The chlordane composition was prepared and applied in the same manner, except that the powder contained four parts of 'clay and one part of chlordane and was dispersed in water in the proportion of five pounds of powder to 100 gallons of Water to pro duce the same proportion of toxicant per 100 gallons of water. Table II shows the percent reduction in grasshopper population in the infested area after the indicated number of days.

TABLE II Percent reduction in grasshopper population on clover after treatment with [dodecachlorotetrahydro-4,7 methanoindene] hexachlorocyclopentadene 'dimer Percent Reduction in Grassho per Population After (Days Treatment [DTM] HCPD, 257 4# 84.1 95. 5 09.1 94.4 96. 7 100 Chlordane. 20% 5# 96. 4 98.9 99. 5 96.7 97. 6 96. 5

above and allowed to stand until August 6 when cages containing 50 grasshoppers were placed over four square feet of each of the treated areas and over a like untreated area. The percent dead ve days after exposure to the treated clover in each case is shown in Table IH below:

4 TABLE nl Effect of [dodecachlorotetrahydro4,7methanoindene] the hexachlorocyclopentadiene dimer on grasshopper infestations occurring 17 days after application to follage No. N o. Pert Treatment (lbs. per acre) Hop- Alive cent Feeding pers Alter 5 Kill Days DTM] HC'PD, 25% 4# 50 9 B2 Slight.

hlordane, 20% 5# 50 34 32 Complete defellation. Check (no toxicant) 50 48 4 Do.

Effect of [dodecachlorotetrahydro4,7methanoindene] the hexachlorocyclopentadiene dimer on infestations of grasshoppers on grass occurring immediately after treatment No. No. Dead Percent Treatment Hoppers After 4 Dead Days [DTM] HC'PD, 5% Dust 5o 43 s6 Chlordane, 5% Dust 50 39 78 Check (no toxicant) 5l) 3 6 In Table V below are shown the results of tests of the residual activity of the [dodecachlorotetrahydro-L- methanoindene] hexdcklorocyclopenradiene dimer in' comparison with chlordane In this test, 50 fresh grasshoppers were caged over portions of grass treated as indicated for the test of Table IV, four days after treatment. Approximately one inch of rain fell the day before the infestation with grasshoppers. The table shows the nurnber and percentage dead four days after infestation.

TABLE V Residual activity of [dodecachlorotetrahydro-4,7meth anoindene] the hexachlorocyclopenladiene dimer against grasshoppers OD gIaSS No. Hop- No. Dead Percent Treatment pers fter 4 Dead Days [DTM] HC'PD, 5% Dust 50 12 24 Chlordane, 5% Dust 50 10 20 Check (no toxicant)- 50 0 0 In Table VI below are shown eld laboratory tests of [dodecachlorotetrahydro-4,7-methanoindene] the hexachlorocyclopentadiene dimer against grasshoppers in comparison with chlordane and toxaphene, the latter being a chlorinated camphene product. In these tests, cranberry bean plants were dusted with compositions containing 3% chlordane, toxaphene and [dodecachlorotetrahydro-4,7methanoindene] the hexac/zlorocyclopenadiene dimer, respectively, with 97% of clay, using the vacuum method in which the plants are placed in an air tight receptacle together with the dust which is spread on a small platform or holder directly under the evacuation tube of the receptacle` The receptacle is then evacuated, after which the vacuum is quickly released, whereupon the dust is uniformly spread over the test plant by the incoming air stream. Adult grasshoppers of the Mclanoplus femur-rubrurn species, collected in the eld, were conned to the treated plants by means of 6" spherical 16 mesh screen cages and allowed to feed. Table VI shows the mortality of the grasshoppers after l, 2, 3, 4 and 5 days on plants subjected to varying dosages of the several toxicants. Foliage consumed by grasshoppers was about equal with [DTM] HCPD and chlordane Significantly more feeding occurred on toxaphene dusted plants.

TABLE V1 Toxic effect of [dodecachlorotetral1ydro-4,7-methanoindene] the hexachlorocyclopentadiene dimer and two commercial grasshopper toxicants against grasshoppers in iield laboratory tests on cranberry bean plants Dust Percent Kill i Hoppers After- N o. Treatment Charg Hoppers Mlg. 1 day 2 days 3 days 4 days 5 days [DTM] HCPD,3% Dust.

Ohlordane, 3% Dust.

Toxaphene" mdmdammmmmmdld) sngswppppps: 010590000000000 Check The eectiveness of the [dodecachlorotetrahydro-4,7 rnethanoindene] hexachlorocyclopentadiene dimer against carpet beetle larvae (Attagenus piceus Oliv.) whose darnage is commonly referred to as moth damage is indicated by the following tests carried out according to ASTM Method D-5S2-49T, entitled Tentative Methods of Tests for Resistance of Textile Fabrics and Yarns to Insect Pests, published in ASTM Standards for 1949, part V, pages 1294134. In the first test, a 2.28% deposit of [dodecachlorotetrahydro-4,7-methanoidene] the hexachlorocyclopentadiene dimer applied to wool from a 1% acetone solution followed by drying, resulted in 100% .kill of carpet beetle larvae allowed to feed thereon within -a two weeks exposure period, with 91.8% protection to the fabric, i.e. with only 8.2% `loss of weight of the original cloth swatchfrom feeding of the larvae.

In a second test, the same swatch, with no further treatment, retested with fresh larvae after eight months storage, again exhibited 100% kill and 95% protection against the larvae indicating no loss of toxicity on storage.

A test similar to those described above was run in which 1.3% of [dodecachlorotetrahydro-llJ-methanoindene] the hexachlorocyclopentadiene dimer was deposited on wool from a 0.5% acetone solution. After eight months storage, the treated Wool was exposed to carpet beetle larvae as before. 100% of the larvae were killed, the deposit effecting 97% protection of the Wool.

While the above describes the preferred embodiments of my invention, it Will be understood that departures may Ibe made therefrom Within the scope of the specication and claims.

I claim:

1. A new insecticidal compositioncomprising `dodecachlorotetrahydro-4,7rnethanoindene] a hexachlorocyclopentadene dimer having the empirical formula CwCllZ, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrograms shown at benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns; together with a dspersing agent and an inert liquid adjuvant as carrier for the insecticide.

3. A new insecticidal composition comprising [dode'cachlorotetrahydro-4,7methanoindene] a hexachlorocyclopentadz'ene dimer having the empirical formula CloClIg, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns; together with a dispersing agent and an inert insecticidal dust adjuvant as carrier for the insecticide.

4. An insecticidal dust adapted for the control of insects of the order Orthoptera comprising a mixture oi' at least about 0.5% of.[dodecachlorotetrahydro-4,7meth anoindene] a hexachlorocyclopeniadiene dimer having the empirical formula C10Cl12, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably sol- Y able at elevated temperatures in the lower aliphatic al- 7 prising a mixture of at least about 0.5% of [dodecach1orotetrahydro-4,7-methanoindene] a hexachlorocyclopentadiene dimer having the empirical formula CZDCIIZ, the property of subliming `without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic tb-- sorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns ana' 15.4 microns an inert dust insecticidal adjuvant as carrier for the insecticide and a wetting agent.

6. An insecticidal wettable spray powder suspension adapted for the control of insects of the order Orthop tera comprising a mixture of at least about 0.5% of [dodecachlorotetrahydro-4,7-methanoindene] a hexachlorocyplopentadiene dimer having the empirical formula CmCllZ, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns a'nd 15.4 microns and an inert dust insecticidal adjuvant as the carrier for the insecticide suspended in an inert liquid insecticidal adjuvant as the carrier for the insecticide.

7. A method for controlling insects which compri-ses contacting said organisms with a composition containing as the essential toxic ingredient [dodecachlorotetrahydro-4,7-methanoindene] a hexachlorocyclopentadiene dimer having the empirical formula CwClIZ, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns.

8. A method for controlling grasshopper infestations on eld crops which `comprises contacting grasshoppers with acomposition containing as the essential toxic ingredient, [dodecachlorotetrahydro-4,7methanoindene] a hexachlorocyclopentadiene dimer having the empirical formula CMCIIZ, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated -temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns.

9. A method for controlling carpet beetle damage on wool which comprises impregnating the wool with a composition containing as the essential toxic ingredient, [dodecachlorotetrahydro4,7methanoindene] a hexachlorocyclopentadiene dimer lhaving the empirical formula CIOCIIZ, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcoholsl having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns.

l0. A method `for controlling ygrasshopper infestations on ield crops which comprises applying to the crops a dust comprising between about 0.5 and about 30% of [dodecachlorotetrahydro-4,7-methanoindene] a hexachlorocyclopentaa'iene dimer having the empirical formula (2106112, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcoholsA having 2 or'more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns and an inert dust insecticidal adjuvant as the carrier for the insecticide, at the rate of between about 1A; lb. and about l lb. of toxicant per acre.

ll. A method for controlling grasshopper infestations on eld crops which comprises applying to the crops a liquid suspension comprising between about 0.5% and about 30% of [dodecachlorotetrahydro-4,7-methanoindene] a hexachlorocyclopentadiene dimer having the empirical formula CmClIZ, the property of subliming without melting at temperatures above aboutv 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns based on the solid content of the composition and an inert dust insecticidal adjuvant as the carrier for the insecticide suspended in a liquid insecticidal adjuvant as the carrier for the insecticide at the rate of between about Vs pound and about l pound toxicant per acre.

12. A method for controlling grasshopper infestations on eld crops which comprises applying to 'the crops a liquid suspension comprising between about 0.5% and about 30% of [dodecachlorotetrahydro-4,7-methanoindene] a hexachlorocyclopentadiene dimer having the empirical formula C10Cl12, the property of subliming without melting at temperatures above about 240 C., being soluble in benzene, acetone, kerosene, carbon tetrachloride, insoluble in methanol and appreciably soluble at elevated temperatures in the lower aliphatic alcohols having 2 or more carbon atoms, having the infrared spectrogram shown at A and B in the drawing and having characteristic absorption peaks at the wave lengths 8.7 microns; 8.9 microns; 9.5 microns; 10.4 microns; 11.3 microns; 12.2 microns and 15.4 microns based on the solid content of the composition and an inert dust insecticidal adjuvant as carrier for the insecticide, suspended in water.

References Cited in the tile of this patent or the orglnal patent 2,519,190 Hyman Aug. l5,A 1950 2,548,509 Yowell Apr. 10, 1951 2,561,209 Kittleson et al. July 17, 1951 2,616,825 Gilbert et al Nov. 4, 1952 2,724,730 Johnson Nov. 22, 1955 OTHER REFERENCES I. A. C. S., 7l, 954 (1949). 

